The Self Interaction Correction

revisited

Ä Explicit dynamics of clusters and molecules under irradiation

Ä Spectroscopic accuracy at low energy

SIC problem : one electron interacts with its own mean-field !

Ä Density Functional Theory (DFT) for electrons, classical ions

Ä From Local Density Approximation (LDA) to SIC and beyond

Toulouse-Erlangen collaboration (P. G. Reinhard)

 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
 About electronic systems

¾ (Quantum) electrons and (classical) ions in molecules

z « Who » follows « whom »
Ex: Born Oppenheimer surface
z Large « phase » space for deformations
Ex: degeneracy lifting
z Well defined center of mass (ions)

¾ Key role of electron exchange (and correlation)

z neutral systems
z most binding comes from exchange (~3/4)
and correlation (~1/4)
Ex: infinite jellium metal
Ex: also in finite systems
 Some observables

¾ Intrinsic single particle properties

Density of states (DOS), Band Gap, Ionization Potential (IP)
Ex: solids (DOS, gap), molecules, chemistry (IP)

¾ Global structure properties

Bond length, Dissociation energy, Potential barriers …
Ex: potential energy surfaces in chemistry

Typical ingredients
¾ Response to electromagnetic fields
for
Static and dynamical responses irradiation dynamics
Polarizability, Magnetic moment, Optical response…
Ex: physics and chemistry of irradiation
 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
 From DFT to LDA ¾ Electrons

z (Time Dependent) Density Functional Theory (TD) DFT

Ensemble of (orthonormal) orbitals (1 electron)
One body density

Effective mean field theory

Hartree Exch. + Corr.

z Local Density Approximation
LDA and TDLDA Î Exchange-correlation function of density ρ
 Local Density Approximation (LDA)
Plasmon response
¾ E electron gas
Local exchange-correlation taken from infinite
Uxc assumed to be a function of ρ (r)
Ex: pure exchange Æ ρ 1/3 ωe d
De
A priori not valid for rapidly varying ρ (r) …
24%
¾ Much better than expected CI
re
Æ Error cancellations between exchange3%
and correlations…
Ex: problem with exact exchange functionals…
1% for global energies
Æ In general correct Vlasov
Ex: IP from E(N+1) – E(N), dissociation energies within 10-20%
Æ Exhibits good formal features
Æ Many sucessful applications (solid state, molecules, clusters)

¾ LDA tends to delocalize wavefunctions Æ metals (simple ones !!)

 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
 From DFT to LDA But… ¾ Electrons

z (Time Dependent) Density Functional Theory (TD) DFT

Ensemble of (orthonormal) orbitals (1 electron)
One body density

Effective mean field theory

Hartree Exch. + Corr.

z Local Density Approximation
LDA and TDLDA Î Exchange-correlation function of density ρ

Energy Î Potential

Self Interaction
Ionization Potential Problem…
 The Ionization Potential Problem

¾ Potential and level scheme

Example of
anion clusters : K7-
(8 electrons)
IP

Exp:
Little bound system
Ionization Potential about 1 eV

LDA : Almost no binding

Totally wrong IP (reasonable ΔE) Æ dynamics ?
 The Ionization Potential Problem (2)
12
Example of organic
10

Io n iz a t io n P o t e n t ia l [ e V ]
molecules:
Exp
Benzene-like cyclic 8
structures:
H Æ N, O, S 6
4 LDA
Neutral species
Covalent bond 2 C6H6 C4H4N2 C4H4S
C5H5N C4H4O

0
50% error on IP !

F u lv e n e

P y r id in e

P y r im id in e

F u ra n e

T h io p h e n e
P y r a z in e
B en zen e

LDA : Totally wrong IP

 Self Interaction Correction (SIC)

¾ SIC energy functional

Subtract explicitely self interaction

¾ One-body equations

,α

Orbital dependent field

Loss of orthonormality …
Time dependent formulation ?

Approximation by One potential: Optimized Effective Potential

NB: No SIC problem in HF due to exact cancellation by exchange

 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
 Optimized Effective Potential (OEP)

¾ SIC and beyond

Try to restore a common 1-body potential by « optimal » choice
of a unique common V0 : « parametrize » wavefunctions ϕi by V0
» …
fu l
ai n
« p
E P
l l O
Fu
 Optimized Effective Potential (OEP)

¾ SIC and beyond

Try to restore a common potential by « optimal » choice of a
unique common V0 : « parametrize » wavefunctions ϕi by V0

¾ Practically

Almost only approximate versions of OEP are numerically tractable…

KLI, Slater, ADSIC…
From full OEP to …

Krieger Li Iafrate (KLI)

A
pp « Local » Average (Slater)
ro
x.
O
EP

« Global» Average

Averaged Density SIC (ADSIC)

 Back to anion clusters

¾ Potential and level scheme

Example of
anion clusters : K7-
(8 electrons)
IP

Exp:
Little bound system
Ionization Potential about 1 eV

Correct IP, restoration Koopmann’s theorem

Access to 1-photon processes (anions)
 Back to carbon cycles

Case of 12
ADSIC
10

Io n iz a t io n P o t e n t ia l [ e V ]
Organic molecules
Exp
8
Good reproduction
6
of IP 4 LDA

with ADSIC 2 C6H6 C4H4N2 C4H4S

C5H5N C4H4O

0
F u lv e n e

P y r id in e

P y r im id in e

F u ra n e

T h io p h e n e
P y r a z in e
B en zen e

ADSIC : Correct IP
 Orthonormality violation
New bad surprises …

Potential energy surface Time variation of energy

Localization/delocalization?

C2
Na5

exact exch.

Violation of
Dissociation problem Energy conservation…
Polarizability problem Momentum conservation…
 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
 SIC revisited
¾ New variational principle
¾ One-body equations (Key) Symetry condition Orthonormality

¾ Double set of wavefunctions

z Idea: Exploit a left over degree of freedom : unitary transform
z Localized vs physical wavefunctions
Symetrizing vs diagonalizing wavefunctions
z Several new possibilities
Application to OEP Æ Generalized Slater becomes accurate
Time dependent calculations in full SIC possible
 Single electron density
OEP with double set:
« Diagonalizing set »
Generalized Slater

« Natural » Slater approximation on

« localized » wavefunctions ψα
Total XY
Generalized Slater (GSlat)

« Localized set »
 Energy and polarizability
Generalized Slater of Carbon atom
Exchange only calculation
Potential energy surface Hartree-Fock exact « 0% »

Polarizability deviation Energy deviation [%]

10 C atom
8

C2 6
exchange only

r
30 x,y
z

20

10
GSlater ≈ full SIC ≈ HF
0
GSlater and SIC restore

Slater

GSLAT
dissociation properties of C2
LDA

SIC
 Polyacetylene

Application to
Polarizabilities
H4 chains

Transverse
Standard DFT test case
Hydrogen chains

H4

Longitudinal

GSlater ≈ full SIC

H2-H2 distance
 Electronic systems
DFT and Local Density Approximation (LDA)
Summary
From Density Functional Theory (DFT) to LDA
LDA
Self Interaction problem
Ionization potential problem
Self Interaction Correction (SIC) Problem
Optimized Effective Potential (OEP)
Simple approximations, Slater, ADSIC Solution
Examples of application
Defects of simple approximations Problem
SIC revisited
General SIC formulation Solution
Double set formulation and Generalized Slater
Time Dependent SIC
Time Dependent SIC (TDSIC)

¾ Variational principle

Orthonormality
¾ TDSIC equation

Å Symetry condition

Å Propagation, puzzle
 2 sets of wavefunctions
TDSIC made practical linked by a
unitary transform
¾ Propagation scheme

Choice :

Propagating set

Symetrizing set

¾ An example from
molecular physics
Simple 1D dimer

Benchmark SIC calculation

 Some conclusions and perspectives

¾ From LDA to SIC and beyond

z SIC schemes solve the electronic IP problem
z Several difficulties remain: formal and numerical challenges
z Localized vs delocalized wavefunctions
z GSlater provides an appealing alternative to OEP
z Full TDSIC provides the first benchmak calculation

¾ Applications
z cluster dynamics from linear to non linear domain
Ex: optical response, photoelectrons spectra,
pump/probe dynamics …
z dynamics of organic molecules
Ex: irradiation of biological molecules …
Thank you

for your
attention